Petroleum sulfonic acid foam control composition and its use

ABSTRACT

THE PRESENT INVENTION IS DIRECTED TO A COMPOSITION AND ITS USE FOR THE CONTROL OF FOAM IN AQUEOUS SYSTEMS AND IN PARTICULAR PULP AND PAPER MAKING SYSTEMS. THE METHOD GENERALLY COMPRISES ADDING TO THE AQUEOUS SYSTEM A COMPOSITION COMPRISING A WATER-INSOLUBLE ORGANIC LIQUID, AN ESTER OF POLYETHYLENE GLYCOL, A PETROLEUM SULFONIC ACID AND A TALLOW FATTY ACID AND/OR TALLOW FATTY ALCOHOL.

United States Patent 3,751,373 PETROLEUM SULFONIC ACID FOAM CONTROLCOMPOSITION AND ITS USE Hillel Lieberman, Andalusia, and Anthony J.Gralfeo, Willow Grove, Pa., assignors to Betz Laboratories, Inc.,Trevose, Pa.

No Drawing. Filed Dec. 29, 1970, Ser. No. 102,553 Int. Cl. B01d 17/00US. Cl. 252--321 13 Claims ABSTRACT OF THE DISCLOSURE The presentinvention is directed to a composition and its use for the control offoam in aqueous systems and in particular pulp and paper making systems.The method generally comprises adding to the aqueous system acomposition comprising a water-insoluble organic liquid, an ester ofpolyethylene glycol, a petroleum sulfonic acid and a tallow fatty acidand/or tallow fatty alcohol.

BACKGROUND OF THE INVENTION As is well-known in the paper makingindustry, foam is an undesirable by-product which is encountered indifferent areas of the paper-making process. In any system where thereis an aqueous medium which contains both dissolved and undissolvedsolids and where there is a great deal of agitation, foam is a potentialproblem. Since paper-making processes meet with all of theprerequisites, the systems are constantly being plagued by foam.Accordingly the industry is constantly seeking out new materials toeither prevent or control foam during the paper-making process since thepresence or absence of foam not only bears directly on the quality ofthe paper produced but also upon the economics of the process.

In this regard one might consider the Fourdrinier machine which althoughbasically an excellent paper making system can be put out of operationby and until foam problems are brought within reasonable control.

Also of importance is the fact that although the foam situation may notbe sufliciently severe to shut-down the machine, it may be so severe asto drastically affect its production speed. To mill personnel, this isnot satisfactory since production is required to meet certain demandsnot only from the stand-point of quality but also from the stand-pointof tons produced.

Areas in the Fourdriner machine where foam may become a problem, areareas such as the headbox, on the wire itself, the wire-pit, seal pitsfrom the suction boxes and rolls, drop-leg and tray run-off, saveall,blend chest and machine chest.

One of the major finished products of integrated kraft pulp and papermills is linerboard and linerboard is generally produced on largeFourdrinier Machines with dual headboxes. While most linerboard is madeentirely from unbleached kraft with a minimum of additives (generallyonly rosin size and alum for pH adjustment), occasionally a better gradeof linerboard is produced in which the top sheet, that portion of theboard supplied by the second headbox, is of bleached or semi-bleachedkraft. Foaming or air entrainment problems are frequently encountered onlinearboard machines. In some cases the foam problem may occur ahead ofthe machine in the stock preparation system where it may be manifestedby difficulty in pumping the stock. However, the most common foamingproblems encountered in the production of linerboard are on the machineitself.

Foam and/or entrained air can cause bubbles on the wire, interferencewith drainage of water through the wire, breaks and uneven drying orpoor moisture profile across the sheet. Foam formation in the wire pitcan also 3,751,373 Patented Aug. 7, 1973 ice be a problem if the foambuilds up to the point where it can touch the underside of the wire.Also it may be objectionable from an esthetic viewpoint or because thepresence of such foam may have a disturbing influence on the operatorswho feel that something must be wrong when they see it. Although somemills do not feel that wire pit foam is harmful, it can entrap varioustypes of debris that could contribute to problems in other areas of themachine system.

In most linerboard defoamer applications, continuous feed is requiredalthough some mills find that they require defoamer for only certaingrades. In the majority of applications, the point of application is thewire pit or the suction side of the fan pump. Most mills feed thedefoamer neat from the drum utilizing a diaphragm pump, sized to coverthe maximum feed rate anticipated. Aspirator devices such as theFeedrator also can be used to feed the defoamer directly into a waterline which then can be introduced to any desired point in the system.Some linerboard mills feed defoamer by gravity to the wire pit but thismethod of feed leads to very poor control.

In some linearboard applications the defoamer may be fed ahead of themachine at a point such as the machine chest or even ahead of therefiners. In such applications it may or may not be necessary to feed anadditional amount of defoamer directly to the machine itself. Ingeneral, since the defoamer will tend to lose efficiency as it passesfurther along in the system, a lower total performance cost will beobtained feeding at one point in the stock preparation system with asupplementary feed at the machine rather than feeding enough at the onepoint ahead of the machine to control foam in the stock preparationsystem as well as on the machine.

Accordingly it was the present inventors goal to not only develop a foamcontrol composition which was effective for the purpose but one whichcould also be fed easily and preferably automatically as with precisionpumps.

The present inventors ascertained that the goals could be achieved witha composition comprising on a weight basis;

(i) from about 0.5% to about 30%, and preferably 2% to 15% of a tallowfatty acid having from 12 to 24 carbon atoms (preferably 16 to 18),and/or a tallow fatty alcohol having from 12 to 24 and preferably 16 to18 carbon atoms;

(ii) from about 0.3% to about 20%, and preferably 0.3% to 4% of apetroleum sulfonic acid having a molecular weight from 400 to about 900,and preferably 400 to 500;

(iii) from about 0.1% to about 15% and preferably 0.5 to 12% of at leastone mono or diester of polyethylene glycol with a fatty acid having fromabout 14 to 18, and preferably 16 to 18 carbon atoms; and preferablyhaving a ethylene oxide content to produce a molecular weight of from300 to 600;

(iv) from about 65% to 95%, and preferably to 93% of a water insolubleorganic liquid such as vegetable oils, aliphatic hydrocarbons, alicyclichydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons,halogenated alicyclic hydrocarbons, halogenated aromatic hydrocarbons,long chain amines and the like.

The composition may additionally contain from about 0.5% to about 8% andpreferably from about 2% to about 6% of a lower alkanol solubilizingagent such as the one to six carbon alcohols i.e. methanol, ethanol,isopropanol and hexanol.

Agents of this nature are used to provide cold temperature stability inthose areas and applications which require this feature. The foregoingrecitations relative to the composition, although the most effective arenot necessarily the only percentages of each that may be utilized. Thepercentages recited represent the desirable ranges from both aneffectiveness point of view and an economics point of consideration.

The effective and economic treatment levels for the inventivecomposition were determined to be within the range of from about 0.01%to about 1% b weight of the foam controlling composition based upon theweight of the dry solids content of the aqueous system. Although, asexplained above, many factors can cause or contribute to the production,existence and maintenance of foam in an aqueous system, the prime factoris considered to be the solids content of the system. In many instancesthis factor has been used in the industry to approximate treatmentlevels. However the most general practice is to add on a weight basisfrom about 1 to about 100 parts of the composition per million parts ofthe aqueous systern, since most foam problems are controlled usingtreatment levels within this range. Although treatment levels above 1%,based upon solids content or 100 p.p.m. based weight of system, arequite effective in controlling foam, the use of excesses above theselevels are prohibitive due to economic considerations. Accordingly theupper treatment level is predicated upon cost consideration rather thanlimit of effectiveness.

As a further explanation or description of the ingredients of thecomposition the following will be of help.

The tallow acids are basically the saturated and unsaturated mono anddicarboxylic fatty acids having from about 12 to 24 carbon atoms, andpreferably 16 to 18 carbon atoms such as stearic acid, palmitic andoleic acid and mixtures thereof. In many instances the tallow acids asobtained are in fact mixtures of various fatty acids such as mixtures ofpalmitic, stearic and oleic acids. Likewise the tallow alcohols havefrom about 12 to 24 but normally from 16 to 18 carbon atoms.

Petroleum sulfonic acids and the metallic salts thereof e.g. calcium,magnesium, potassium and sodium salts, are usually obtained as aby-product of white oil manufacturing and lube stock refining, usuallyby the addition of sulfur trioxide to oils. The molecular weights ofthese particular derivatives range from about 400 to 900. Products ofthis type are obtainable under the trade names of Petronate HL andcalcium Petronate.

The polyethylene glycol derivatives are those esters such as themono-oleate, dioleate, mono and distearate, mono and dipalmitate esters.Moreover the derivatives may be the 300 to 600 derivatives such aspolyethylene glycol 600 dioleate or the polyethylene glycol 300monoleate. The number which appears after the polyethylene glycol inthese designations represents the degree of polymerization of thepolyethylene glycol. More specifically, this number indicates that thenumber of ethylene oxide units in the polymer is such as to yield atotal molecular weight expressed in the number of the polymerdesignation.

The water-insoluble organic liquids which can be advantageously used inthe composition are the vegetable oils, such as the water-insolubleedible oils which are extracted from seeds and which are generallconsidered to be mixtures of glycerides, the aliphatic hydrocarbons, thealicyclic hydrocarbons and the aromatic hydrocarbons and the halogenatedderivatives thereof. These generic descriptions include many typecarriers or liquids such as benzene, hexane, octane, mineralhydrocarbons such as the mineral oils (parafiinic oils, naphthenic oils,halogenated products thereof and kerosene). Mineral seal oil and similarpetroleum fractions, synthetic polymers and halogenated productsthereof, such as the liquid trifiuorovinyl chloride polymers, long chainalcohols such as nonyl alcohol and octyl alcohol, long chain esters suchas diglycol laurate, and long chain amines such as octyl amine, nonylamine and 2-ethyl-amino-heptane. In many instances these liquid carriersare not only water-insoluble but also hydrophobic.

The carrier liquid should be of such nature that its boiling pointshould be greater than 150 F. and its viscosity should be such as to beliquid at room temperature. In the case of mineral hydrocarbons aviscosity of about 30 to 400 SUS F.) has been found to be completelyacceptable. From the vast number of water-insoluble liquids evaluated,it would appear that any liquid which possesses the aforementionedproperties would be operable.

Spreading agents or surfactants which are commercially available such assorbitan monostearate and the surfactants, decyl alcohol, silicone oils(Union Carbides L45) and the polyether triols of high molecular weight(Union Carbides LHT42) have been used successfully in the inventivecompositions. These agents are generally included where rapiddistribution of the defoamer in a particular system is required.

The composition of the invention can be made simply by mixing theingredients thoroughly, heating the mixture to a temperature of fromabout to F. for a time to insure that the ingredients have beendissolved and thoroughly incorporated. The blend is then cooled slowlyto 100 F. and at this point other ingredients such as the solubilizingagent may be added. The product is then ready for use. The heating ismerely an expedient in the preparation, since products prepared withoutheating but with longer mixing times operate as effectively.

In order to determine the foam controlling capacity of the compositionof the present invention, a test procedure was used which placed thesample stock solutions under agitation conditions similar to thoseexperienced in the actual paper making process.

In order to more accurately assimulate the condition of a papermakingprocess, actual stock samples are either obtained directly from papermills or the tests were conducted in the mill proper. These stocksamples were approximately 0.5% consistency. More specifically, thestock is comprised of approximately 99.5% aqueous medium andapproximately 0.5% fiber, filler, coloring agent, etc. The stock is thatwhich would be fed from the headbox of a paper-making machine to theFourdrinier wire Where paper or linerboard formation initially occurs.

The test procedure used required 600 milliliters of the stock solution.

TEST PROCEDURE The stock is circulated from a calibrated reservoirholding the stock to and through a pump and back to the reservoir. Thisaction agitates the stock and simulates the conditions which arenormally encountered during the paper making process. The reservoir iscalibrated in centimeters in order to measure the foam height at varioustime intervals which is a mode of measuring the degree of foaming of asystem or in other terms, the defoaming or antifoaming action of thecomposition. The height of the foam is noted at various intervals andthe longer the time required for the foam to reach a certain level thebetter the inhibiting properties of the composition. The calibrations ofthe reservoir range from 0 to 300 centimeters with the normal slurryvolume taking up the first 100 cm. A reading therefore of 100 means thatessentially no foam formed during the respective period. The lastreading is made when the foam overflows the reservoir or exceeds the 300centimeter level.

When the overflow takes place, the pump is then turned oif. The test isan excellent measure of the defoaming characteristics of a compositionsince it is quite stringent.

SPECIFIC EXAMPLES In order to illustrate the effectiveness of thecompositions of the present invention, the following compositions wereprepared and tested in accordance with the test procedure outlinedearlier. In order to accurately compare the various compositions, thecompositions were all prepared in the same manner so as to avoid anyvariations in the composition other than the ingredients and theconcentrations thereof. In order to obtain the best comparisons, theingredients were, where desirable, kept the same.

The products were prepared by merely blending and mixing the ingredientsand heating the blend at a temperature of 145 F. for a time suflicientto dissolve all of the soluble ingredients and to homogeneously mix theingredients (e.g. 15 minutes). The composition was then allowed to cool,after which the lower alkanol, if used, was added and thoroughly mixedin and the product or composition was then ready for testing or use.

Example 1 The composition of this example contained the followingingredients in the respective percentage by weight listed:

Percent Kerosene. 79 Polyethylene glycol 600 dioleate 14 Tallow fattyacid (HCP, a mixture of primarily palmitic, stearic and oleic acids)Isopropanol 5 Example 2 The composition of this example was the same asExample 1 excepting that it contained 2% of a petroleum sultonic acid(Petronate HL) having a molecular weight ranging from about 400 to 460,an empirical formula of C H SO H, and an S content of about 17.5%. Theamount of kerosene was proportionally decreased i.e. the compositioncontained 77% kerosene.

Example 3 The composition of the example contained:

Percent Acme S-l (a paraflinic oil having an SUS of 105 at 100 F.) 79Polyethylene glycol 600 dioleate 14 Tallow fatty acid (mixture ofprimarily palmitic, stearic and oleic acids) Isopropanol 5 Example 4 Theproduct was essentially the same as Example 3 except in that itcontained 2% Petronate HL (see Example 1) and the polyethylene glycol600 dioleate content was reduced to 12%.

Example 5 This product was essentially the same as that of Example 4excepting that it contained 3% Petronate HL and the Acme S-lOS contentwas reduced to 78%.

Example 6 The composition of this example contained:

Percent Reprol (a paraifinic oil having an SUS of 40 at 100 Example 7The composition of Example 6 excepting that it contains 2% Petronate HLand the Reprol content was reduced to 77%.

6 Example 8 The composition of this example contained:

Percent Reprol 76 Calcium Petronate (basic calcium salt of petroleumsulfonic acid and having a molecular weight of about 892) 3 HCP (noteExample 1) 7 Sorbitan monostearate (surfactant) 0.5 Polyethylene glycol600 monostearate 0.5 Alfol 1618C (see Example 6) 7.0 Isopropanol 6.0

Example 9 The composition of Example 8 excepting that Sodium Petronatewas used in place of the Calcium Petronate. Sodium Petronate is thesodium salt of the petroleum sulfonic and the sodium Petronate has amolecular weight of about 450.

Example 10 This composition contained:

Percent Topas S-lOS (an oil composed of a mixture of paraffinic,naphthenic and aromati oils), SUS of at 100 F. 79 HCP (note Example 1) 8Alfol 1618C (note Example 6) 3 Polyethylene glyol 400 dioleate 2Polyethylene glycol 300 dioleate 2 Isopropanol 6 Example 11 Thiscomposition was essentially the same as that of Example 10 exceptingthat it contained 3% Petronate HL (see Example 1) and the oil contentwas reduced to 76% TESTS TABLE 1 Foam height after designated intervalsin cm. Mill location from Composition which stock 30 60 90 Time (sec.)of sample obtained see. sec. sec. sec. of overflow 1 Example 1.... A S.Carolina mill 14. 5 Example 2 -.do 170 Example 3. 26. 0 Example 4. 81.3Example 5. o... 106. 6 Example 6.... A Maryland milL- 30. 0 Example 7..do Example 6.-.- A Michigan mill 29.0 Example 7 ..do 225 270 62.0Example 6..-- A Georgia mi 265 34. 0 Example 7 ..do 176 195 Example6...- A Michigan mill.-. 255 37. 0 Example 8 ..do 160 205 245 118i ()1Example 9 -do 73. 0 Example 10..- A Georgia mill.. 56. 3

Example 11 ..do

. 1 Time required for team to exceed 300 em, if measured.

1 N at measured.

From the foregoing tabulated results it is apparent that in everyinstance, the products containing the petroleum sulfonic acid or itsmetallic salt out-performed the products which were formulatedessentially the same but did not contain the sulfonic acid derivative.The difference in efiectiveness in every case was quite substantial.

Because the test evaluations proved so successful for the inventivecompositions, the following products were formulated together with athird product which did not contain the sulfonic acid derivative. Theseproducts were prepared as described for the earlier examples andcomposition-wise were as follows:

Products I and III were comparativey tested on the actual linerboardproducing machine at a North Carolina mill. For the test all variableswere maintained the same with respect to the paper making operationexcepting the feed rates. In this type test the feed rates to controlthe foam within certain and acceptable limits is the comparisoncriteria. Product I to perform the particular function required a feedrate of approximately 14 cubic centimeters per minute. Product HI on theother hand required a feed rate of 25 cubic centimeters per minute andeven at the feed rate control was sporadic.

Based upon the results of the mill test at the North Carolina mill,Products I and II were on-machine mill tested at a South Carolina millwhich was producing Kraft linerboard. The products were fed at twolocations on the machine, i.e. at the raw stock chest where the pH is9-10 and at the machine chest when the pH is 5.2-5.3. Both Products Iand II, on a cost-performance basis outperformed by 20% to 30% acompetitor antifoam which was also being tested by mill personnel.

From the foregoing then it was evident that the inventive compositionsoperated effectively to achieve the goals demanded.

The foregoing examples were used as illustrations of the invention.Modifications of the invention i.e. increasing or decreasing the contentof the respective materials within of course the range disclosed or thesubstitution of obvious equivalents also operate quite effectively forthe purpose.

Accordingly having described the invention, what is claimed is:

1. A foam control composition comprising on a weight basis:

(i) from about 0.5% to about 30% of at least one tallow fatty acid ortallow fatty alcohol, said acid or alcohol having from about 12 to about20 carbon atoms;

(ii) from about 0.3% to about 20% of a petroleum sulfonic acid having amolecular weight of from about 400 to about 900, or the metal salt ofsaid sulfonic acid;

(iii) from about 0.1% to about 15% of a compound selected from the groupconsisting of polyethylene glycol mono-esters of fatty acids having from14 to 18 carbon atoms, and polyethylene glycol diesters of fatty acidshaving from about 14 to 18 carbon atoms; and

(iv) from about 65% to about 98% of a water-insoluble liquid selectedfrom the group consisting of vegetable oils, aliphatic hydrocarbons,alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aliphatichydrocarbons, halogenated alicyclic hydrocarbons, halogenated aromatichydrocarbons, and long chain amines.

2. A composition according to claim 1 which contains from about 0.5% toabout 8% of a lower alkanol solubilizing agent.

3. A composition according to claim 1 wherein:

(i) the tallow fatty acid or alcohol has from about 16 to 18 carbonatoms and is present in an amount of from about 2% to about 15 (ii) thepetroleum sulfonic acid has a molecular weight of from about 400 to 500and is present in an amount of from about 1.0% to about 8%;

(iii) the polyethylene glycol ester is polyethylene glycol 6'00 dioleateand is present in an amount of from about 0.5% to 12%;

(iv) the organic liquid is a refined mineral oil and is present in anamount of about 75% to about 93%;

4. A composition according to claim 3 which contains from about 2% toabout 6% of isopropanol.

5. A composition according to claim 3 wherein:

(i) the tallow acid is a mixture of stearic, palmitic and oleic acidsand is present in an amount of about 2%;

(ii) the petroleum sulfonic acid is present in an amount of about 2%;

(iii) said glycol ester is present in an amount of about 8%; and

(iv) said mineral is paraflinic and is present in an amount of about83%.

6. A composition according to claim 5 which contains about 5% ofisopropanol.

7. A method of controlling foam in the aqueous system of a kraft pulpand paper mill system which comprises adding thereto an amount effectivefor the purpose of a composition comprising:

(i) from about 0.5 to about 30% of a tallow fatty acid or alcohol havingfrom about 12 to about 20 carbon atoms;

(ii) from about 0.3% to about 20% of a petroleum sulfonic acid having amolecular weight of from about 400 to about 900, or the metal salt ofsaid sulfonic acid;

(iii) from about 0.1 to about 15% of a compound se-- lected from thegroup consisting of polyethylene glycol mono-esters of fatty acidshaving from 14 to 18 carbon atoms and polyethylene glycol diesters offatty acids having from about 14 to 18 carbon atoms; and

(iv) from about 65 to about 98% of a water-insoluble liquid selectedfrom the group consisting of vegetable oils, aliphatic hydrocarbons,alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aliphatichydrocarbons, halogenated alicyclic hydrocarbons, halogenated aromatichydrocarbons, and long chain amines.

8. A method according to claim 7 wherein the compositron contains fromabout 0.5 to about 8% of a lower alkanol solubilizing agent.

9. A method according to claim 7 wherein:

(i) the tallow fatty acid or alcohol has from about 16 to 18 carbonatoms and is present in an amount of from about 2% to about 15%;

(ii) the petroleum sulfonic acid has a molecular weight of from about400 to 500 and is present in an amount of from about 1% to about 8%(iii) the polyethylene glycol ester is polyethylene glycol 600 dioleateand is present in an amount of from about 0.5% to 12%.

(iv) the organic liquid is a mineral oil and is present in an amount ofabout 75 to about 93 10. A method according to claim 9 which containsfrom 13. A method according to claim 10 wherein the comabout 2% to about6% of isopropanol. position is added to the aqueous system in an amountof 11. A method according to claim 9 wherein the; from about 1 to about100 Parts P minion- (i) the tallow acid is a mixture of stearic,palmitic and oleic acids and is present in an amount of about 5References C'ted 2%; UNITED STATES PATENTS (ii) the petroleum sulfonicacid is present in an amount 2,052,164 8/1936 Buc 252-358 ofabvutm;2,544,564 3/1951 Peterson et a1. 252-321 (iii) said glycol ester ispresent in an amount of about 2,668,150 2/ 1954 Luvisi 25232l 8%;and 103,198,744 8/1965 Lamont 252-321 (iv) said mineral Oil is paraffinic andis present in an 1,9 ,641 6/1934 Mathias 25Z321 amount of about 83%. 12.A method according to claim 9 wherein the com- JOHN WELSH PrimaryExammer position is added to the aqueous system in an amount of 5 U.S.C1. X.R. from about 1 to about 100 parts per million. 252-458

